Process for the preparation of a poly(vinyl-acetate-dialkyl maleate-acrylic acid)textile size

ABSTRACT

DISCLOSED HEREIN IS A PROCESS FOR THE PREPARATION OF A POLYVINYL (VINYL-ACETATE-DIALKYL MALEATE-ACRYLIC ACID) TEXTILE SIZE WHICH COMPRISES (1) INTER-POLYMERIZING THE MONOMERS AT A TEMPERATURE OF FROM 40 TO 60*C. TO FORM A LATEX USING A SURFACTANT SYSTEM COMPRISING A PHOSPHATE ESTER OF AN ALKYL PHENOL-ETHYLENE OXIDE CONDENSATE, WHEREIN THE ALKYL GROUP CONTAINS 7 11 CARBON ATOMS; AND (2) DISSOLVING THE RESULTING LATEX IN A SOLVENT TO FORM THE SIZE.

United States Patent PROCESS FOR THE PREPARATION OF A POLY(VINYL-ACETATE-DIALKYL MALEATE-ACRYL- IC ACID) TEXTILE SIZE Albert E.Corey, East Longmeadow, and Donald D. Donermeyer and Joel Fantl,Springfield, Mass., and Charles R. Williams, St. Louis, Mo., assignorsto Monsanto Company, St. Louis, M0.

N0 Drawing. Continuation-impart of application Ser. No. 98,914, Dec. 16,1970, now Patent No. 3,716,547, dated Feb. 13, 1973. This applicationDec. 29, 1972, Ser. No. 319,246 The portion of the term of the patentsubsequent to Feb. 12, 1990, has been disclaimed Int. Cl. C08f 45/30 US.Cl. 260-33.8 UA 16 Claims ABSTRACT OF THE DISCLOSURE Disclosed herein isa process for the preparation of a poly(vinyl-acetate-dialkylmaleate-acrylic acid) textile size which comprises 1) inter-polymerizingthe monomers at a temperature of from 40 to 60 C. to form a latex usinga surfactant system comprising a phosphate ester of an alkylphenol-ethylene oxide condensate wherein the alkyl group contains 7 to11 carbon atoms; and (2) dissolving the resulting latex in a solvent toform the size.

This application is a continuation-in-part of application, Ser. No.98,914, filed Dec. 16, 1970, now US. Pat. No. 3,716,547 granted Feb. 13,1973.

BACKGROUND OF THE INVENTION 1. Field of the Invention The presentinvention relates to a process for the preparation of textile sizes.More particularly, it relates to a process for the latex polymerizationof a poly(vinyl acetate-dialkyl maleate-acrylic acid) textile sizewherein the dialkyl maleate is selected from the group consisting ofdimethyl maleate and diethyl maleate, wherein the resulting latex isdissolved in a solvent to form the size.

2. The Prior Art Polymeric substances are well known in the prior artfor use as textile sizes. In conventional loom operations yarn is sizedwith an aqueous solution of a water soluble material such as a copolymerof vinyl acetate and carboxylic acid, woven into cloth on a conventionalloom with a mechanical shuttle and then the size is removed in a waterbath. While these sizes have been adequate in the past, recentdevelopments in the textile industry have created an increasing demandfor textile sizes with improved tensile strength, elongation, toughness,solubility characteristics, etc.

One such development in recent years is the water jet loom. The waterjet loom employs a jet of water in place of a mechanical shuttle inorder to weave the yarn into a fabric. A water jet loom provides afaster weaving operation and less mechanical abrasion of the yarn. Theresult is an increase in production and improved quality in the wovenfabric.

The size used in water jet weaving operations is customarily appliedfrom aqueous solution. Once it is applied to the yarn and dried, thesize must be sufficiently water resistant so as to remain on the yarnduring the weaving operation. Moreover, in order to be efiicient andeffective, the size must retain its adhesion and film properties such ashigh tensile strength when wet by the water jets in the weaving processwithout becoming soft and slimy. Finally the size must be soluble inmild aqueous alkali solutions or organic solvents so that it can beremoved from the woven fabric. The fore-going properties are the resultof a critical inter-relationship between chemical composition andmolecular weight of the polymeric material which is used as the textilesize.

The sizes of the prior art which are customarily used in conventionalloom weaving operations are found to lag}; the necessary physicalproperties which are required for use with water jet looms.

Thus, there exists in the art a need for a process for the preparationof improved textile sizes which can be used to size yarns which are tobe woven on conventional or water jet looms then removed using either anaqueous alkali solution or an organic solvent.

SUMMARY OF THE INVENTION The above-mentioned need in the prior art isfulfilled by the present invention which provides a process for thepreparation of textile sizes which are suitable for use on bothconventional and water jet looms. More particularly, the presentinvention provides a process for the preparation of a textile size whichprocess comprises (1) interpolymerizing critical amounts of vinylacetate, dialkyl maleate and acrylic acid monomers in a latex system ata temperature in the range of from 40 to 60 C. in the presence of asurfactant system comprising a phosphate ester of an alkylphenol-ethylene oxide condensate; dissolving the resulting latex in anaqueous or organic solvent to form the size.

The polymers prepared in accordance with the procasses of the presentinvention have excellent solubility characteristics and film properties.Moreover, sizes prepared from these polymers are easily removed fromsized yarns or the resulting fabric using aqueous alkali solutions ororganic solvents. Consequently, these polymers are especially suitablefor use as yarn warp sizes for use on conventional or water jet looms.

THE PREFERRED EMBODIMENTS The monomers used in the interpolymerizationprocess of the present invention are vinyl acetate, a dialkyl maleateselected from the group consisting of dimethyl maleate and diethylmaleate and acrylic acid. The polymerization charge comprises from 83 toby weight of vinyl acetate, from 2 to 10% by weight of dialkyl maleateand from 3 to 7% by weight of acrylic acid based on the total weight ofthe monomers. More preferably, the polymerization charge comprises from87.5 to 91% by weight of vinyl acetate, from 5 to 7.5% by weight ofdialkyl maleate and from 4 to 6% by weight of acrylic acid based on thetotal weight of the monomers.

The latex polymerization process of the present invention is carried outat a temperature in the range of from 40 to 60 C. and preferably at atemperature in the range of from 40 to 45 C. At temperatures below about40 C. the polymerization rate is too slow and the recation mass tends tocoagulate. At polymerization temperatures above 60 C. the product is oflow molecular weight and lacks the tensile strength and elongationrequired in sizes for use on water jet looms.

The surfactant system used in the processes of the present inventioncomprises a phosphate ester of an alkyl phenol-ethylene oxide condensatewherein the alkyl group contains from 7 to 11 carbon atoms. Especiallypreferred are the phosphate eters of tertiary octyl phenol-ethyleneoxides condensates (hereinafter referred to as PEOPEO) and the phosphateesters of nonyl phenol-ethylene oxide condensates (PENPEO). Thesepreferred surfactants are available commercially as Triton XQS (Rohm &Haas Company) and GAFAC RE-870 (General Aniline & Film Company),respectively. The amount of the phosphate ester of an alkylphenol-ethylene oxide condensate used 3 in the present invention will bein the range of from 1.0 to 4.0% by weight based on the total weight ofthe latex.

Preferably, the polymerization processes of the present invention arecarried out using an anionic cosurfactant in combination with thephosphate esters of an alkyl phenolethylene oxide condensate. The use ofthe cosurfactants reduces the amount of coagulum in the resulting latexand provides a better product. The preferred-cosurfactants used in thepresent invention include alkyl aryl sulfonates such as sodium dodecylbenzene sulfonate; fatty alcohol sulfates such as sodium lauryl sulfate;dialkyl sulfosuccinates, sodium dihexyl sulfosuccinate; etc.

The amount of co-surfactant used is in the range of 0.1 to 0.3% byweight and more preferably 0.15 to 0.25% by weight based on the totalweight of the latex.

The polymerization processes of the present invention are initiated by atwo component redox free radical initiator system. Suitable oxidingcomponents for the system are the inorganic peracid salts such asammonium, potassium and sodium persulfates, perborates, and hydrogenperoxide. Preferred however, are the oil soluble organic hydroperoxidessuch as t-butyl hydroperoxide, cumene hydroperoxide, p-methanehydroperoxide, etc. and esters of the t-butyl perbenzoate type. Theuseful reducing components include compounds like the sulfites.bisulfites, hydrosulfites and thiosulfites, ethyl and other alkylsulfites; the sulfoxylates, such as sodium formaldehyde sulfoxylate; andthe like. Especially preferred are initiator systems based on t-butylhydroperoxide and sodium formaldehyde sulfoxylate; and redoxcombinations such as mixtures of hydrogen peroxide and an iron salt,hydrogen peroxide and zinc formaldehyde sulfoxylate or other similar'reducing agent; hydrogen peroxide and a titanous salt, potassiumpersulfate and sodium bisulfate and a bromate mixed with a bisulfate.

The use of equimolar amounts of initiator system components is generallypreferred although the amount of each component as well as the totalamount of catalyst used depends on the type of component used as well ason other polymerization conditions and may range between .02 and 0.2% byweight of the total polymerization system, the preferred range being0.02 to 0.06% for tire oxidizing component and 0.04 to 0.1 for thereducing component.

The solids contents of the latices prepared by the processes of thepresent invention can be varied over a wide range. The preferred laticeshaving a solids content in the range of from 16 to 65% by weight andmore preferably from 35 to 55% by weight, based on the total weight ofthe latex.

A latex is prepared in conventional latex polymerization equipment whilemaintaining a nitrogen atmosphere and mild agitation using the followingcharge:

A Charge: Parts Water 62.03 PEOPEO 1.58 Ammonium hydroxide (28%) 0.20Sodium formaldehyde sulfoxylate 0.05

t-butyl hydroperoxide (90%) 0.03 Dimethyl maleate (DMM) 1.75

Vinyl acetate (VOAC) 31.67 Acrylic acid 1.58

The PEOPEO surfactant, ammonium hydroxide buffer solution, sodiumformaldehyde sulfoxylate and the water are charged to a glass linedreaction vessel. The tertiary butyl hydroperoxide polymerizationinitiator is dissolved in the monomeric mixture and eight percent (8%)of the monomeric charge (charge B) is then dispersed in the charge A.The remaining 92% of the monomers (charge B) is added to the reactionvessel by a conventional delayed addition technique over a period of 2%hours. During this time the temperature of the reaction batch ismaintained in the range of from 41 to C. while maintaining mildagitation.

The resulting latex has a total solids of 35.7%, a pH of 4.9 and aBrrokfield viscosity of 23 centipoises. The poly(vinyl acetate-dimethylmaleate-acrylic acid) resin has a specific viscosity of 2.51 whenmeasured as a 1% solution in dimethyl sulfoxide at 25 C. Otherproperties of this latex are tabulated in Table 1 below.

EXAMPLES 2 to 10 The following Examples 2 to 10 are set forth toillustrate variations in the latex polymerization reaction conditions ofthe present invention. In each case the general procedures of Example 1are followed except for the noted changes. The resulting latices havesolids contents in the range of from 35 to 42% by weight of Brookfieldviscosities in the range of from 10 to cps. at 25 C. These examples aretabulated in the following Table 1.

TABLE 1 Summary of Examples 1 to 10 Example 1 2 3 57. 7 57. 87 62. 0362. 03 57. 62. 03 57. 03 62. 03 57. 70 1.58 1.58 1.26 1.58 1. 58 1 581.58 0 20 0 25 O 20 O. 20 0. 20 0 20 0. 20 0 20 0. 20 0. 39 0 20 0 39 a0.18 0.18 Charge B:

Total monomer 35 40.0 40. 0 35. 0 35 0 40. 0 35 40 35 40 Percent vinylacetate 90. 5 86. 65 91. 65 90. 5 86 5 90. 5 90. 5 89. 5 90 5 90 5Percent dialkyl maleate 5. 0 10. 5. 0 5. 0 7 5 5. 0 5. 0 5.0 5 0 5 0Percent acrylic acid 4. 5 3.35 3. 35 4. 5 6 0 4. 5 4. 5 5. 5 4 5 4 5Percent total coagulum 0. 68 0. 02 0. 16 0. 2 0 05 0.15 0. 08 0. 07 0 04Polymer properties:

Specific viscosity 2. 51 1. 38 1.64 2. 31 2. 93 2. 85 2. 92 6.05 2. 782. 58 Tensile/percent elongation' Dry, 65% R H 3,190/288 5, /110 2,350/380 2, 900/283 2, /320 3, 320/370 3, 560/423 3, 040/360 Wet 1,770/442 2, 030/310 1, 520/430 2, 310/541 59 2, 000/574 1, 440/470 Dry,80% R.H

During the polymerization reaction a conventional base such as ammoniumhydroxide or sodium hydroxide is 70 all coagulum produced, bothfilterable and remaining as used to buffer the latex to a pH in therange of 4.0 to 6.0.

The following examples are set forth in'illustration of the presentinvention and should not be construed as a limitation thereof. Unlessotherwise indicated, all parts 75 fouling on the impeller and walls ofthe reactor. This value is measured by recovering the coagulum byfiltration and by scraping from the equipment, drying it,,weighing it,and calculating its percent weight based on the calculated solids.Values in excess of 0.75% indicate that objectionable kettle foulingwould occur in commercial scale batches which would cause seriousproblems in product yields, product handling and equipment clean-up.

Specific viscosity measurements are made on 1% solutions in dimethylsulfoxide at 25 C.

Tensile (p.s.i.) and elongation are measured according to ASTM MethodD-882-67 after conditioning at 65% and 80% relative humidity. The wetvalues are obtained on 4 mil films which are immersed in water for five(5) minutes.

Example 9 uses diethyl maleate as the dialkyl maleate component whileall of the other examples use dimethyl maleate. Examples 1, 4, 5 and 7to 9 use a phosphate ester of an octyl phenol-ethylene oxide condensate(.PEOPEO) while the other examples use a phosphate ester of a nonylphenolethylene oxide condensate (PENPEO). Example 1 uses a singlesurfactant while Examples 2 to use a combination of a major amount ofPEOPEO or PENPEO with a minor amount of sodium dihexyl sulfosuccinate(SDS) which is available commercially as Aerosol MA. from AmericanCyanamid. Note in Examples 2 to 10 that when a combination ofsurfactants is used, the percent total coagulum is significantly lowerthan in Example 1 wherein a single surfactant is used.

Examples 1 to 4 and 7 to 10 are prepared using ammonium hydroxide as thebuffer agent while Examples 5 and 6 use sodium hydroxide. The high wettensile strength of the polymers prepared in Examples 1 to 5 and 7 to 10using ammonium hydroxide, indicate their suitability for use as a sizein a water jet weaving process.

The polymeric products of Examples 2 and 3 contain only 3.35% acrylicacid monomer. These polymers have good water resistance, tensile andelongation making these polymers very suitable for use in water jetweaving processes using organic solvent desizing methods.

In order to be suitable for use as sizes in the water jet weavingprocess the polymeric size must have a good tensile strength, toughnessand adhesion to the yarn under wet conditions. The specific viscositiesof the polymers of the present invention are good indices as to wettensile strength and toughness when considered in the context of thetype and amount of co-monomers present in the polymer. The preferredpolymers of the present invention have a specific viscosity in the rangeof from 1.2 to 12.0 and more preferably in the range of from 1.3 to10.0.

The correlation between specific viscosity of the polymers of thepresent invention and wet tensile strength are shown in the followingTable II wherein five series of polymers are prepared using the generalprocedures of Examples 2 to 10 above. Variations in the amount ofcatalyst and polymerization temperatures lead to variations in thespecific viscosity of the resulting polymers. These polymers are thentested for wet tensile strength and the results are tabulated in thefollowing Table II.

TABLE IL-CORRELATION OF WET TENSILE STRENGTH WITH SPECIFIC VISCOSITYPolymer Wet tensile 1 Polymers are prepared using the following percentby weight mono- F meric charges:

A-vinyl acetate/dimethyl maleate/acrylic acid 91.65/5.0/3.35.1.3-vinylacetate/dimethylmaleate/acrylic acid 90.5/5/4.5. C-vinylacetate/dimethyl maleate/acrylic acid 90/5/5. D-vinyl acetate/diethylmaleate/acrylic acid 90.5/5/4.5. E-vinyl acetate/dibutyl maleate/acrylicacid 91.65/5/3.35. I Tensile values for 0-1 and 0-2 are determined at80% RH.

EXAMPLES 11 to 13 The following Examples 11 to 13 are set forth ascontrol examples to illustrate the effect of polymerization temperatureon the physical properties of the resulting latex. In each eample thegeneral charge and procedure of Example 10 is repeated while thepolymerization temperature is varied. The specific viscosity of theresulting polymer is then measured. The results are tabulated in TableIII below.

TABLE III Summary of examples 11 to 13 Polymerization Specific temp., C.viscosity Example:

1 Run coagulated.

The data in the foregoing Table III indicates that, within the frameworkof the present invention polymerization temperatures below C. lead tocoagulation while increasing temperatures above C. lead to polymers withdecreasing specific viscosities. However, for any given polymer systemwithin the framework of the present invention, optimum specificviscosity is obtained when the polymerization reaction is in the rangeof from 40 to 60 C. and more preferably from 40 to C.

The following Eamples 14 to 19 are set forth to further illustrate thecriticalities of the present invention.

EXAMPLE 14 The general charge and procedure of Example 3 is repeatedhere except that fumaric acid is substituted for the acrylic acid usedin Eample 3. The reactants are mixed and heated. No significantpolymerization reaction has taken place even after 24 hours.

EXAMPLE 15 Example 14 is repeated here except using crotonic acid inplace of fumaric acid. The polymerization is carried out for 5 /4 hours.At the end of this time, the reaction mixture is found to contain 9% byweight of free monomer based on the total latex weight. This lowconversion rate makes the polymer process unacceptable for use on acommercial scale. Moreover, the polymer is found to have a specificviscosity of only 1.1 and is unacceptable for use as a size in a waterjet weaving process.

EXAMPLE 16 In this example 88% by weight of vinyl acetate, 5% by weightof dimethyl maleate and 7% by weight of monomethyl maleate areinterpolymerized according to the general procedure of Example 10.

The monomethyl maleate monomer is being used in place of the acrylicacid used in Example 10. The resulting polymer is found to have aspecific viscosity of 1.8, tensile strength of 1880 p.s.i. dry and 1060p.s.i. wet and elongation of 200% dry and 500% wet. The low wet tensilestrength of this polymer coupled with poor wet adhesion to acetatefibers and film insolubility in aqueous alkali, makes it unacceptablefor use as a size in a water jet weaving process.

7 EXAMPLE 17 In -this example dibutyl maleate is used in place of thedimethyl maleate and diethyl maleate used in Examples 1 to 10 above-Thegeneral polymerization procedures used in Example 1 are followed hereusing 91.65% by weight of vinyl acetate, 5.0% by weight of dibutylmaleate and 3.35% by weight of acrylic acid. The resulting polymer has aspecific viscosity of 1.79, tensile strength of 2050 p.s.i. dry and 680p.s.i. wet and elongation of 230% dry and 240% wet. The low wet tensilestrength of this polymer makes it unacceptable for use as a size in awater jet weaving process.

EXAMPLE 18 In this example methyl methacrylate is used in place of thedimethyl maleate used in Examples 1 to 8 and 10 above. The generalpolymerization methods of Example 4 are used here using a monomer chargeof 89% by weight of vinyl acetate, 5% by weight of methyl methacrylateand 6% by weight of acrylic acid. The reaction mixture coagulated and nopolymer was obtained for testing.

EXAMPLE 19 In this example acrylonitrile is used in placed of thedimethyl maleate used in Examples 1 to 8 and 10 above. The generalpolymerization methods of Example 4 are followed using a monomer chargeof 90% by weight of vinyl acetate, 5% by weight of acrylic acid.

After four hours reaction time only 6.5% of the monomers have beenconverted into polymer.

EXAMPLE This example illustrates the criticality of using a surfactantwhich is a phosphate ester of an alkyl phenolethylene oxide condensate.Example 4 is repeated here except that octyl phenol-ethylene oxidecondensate is used as the surfactant in place of the phosphate ester ofoctyl phenol-ethylene oxide condensate used in Example 4. The octylphenol-ethylene oxide condensate used in this example is a well-knownsurfactant which is available commercially as Triton X-405 from Rohm andHaas. After three hours reaction time the batch was completelycoagulated.

EXAMPLE 21 Example 20 is repeated here except using a surfactant whichis a phosphate ester of an aliphatic alcohol-ethylene oxide condensate.After three hours reaction time the batch was completely coagulated.

PART B.Testing of the Latices of Examples 1 to 5 and 7 to 10 as TextileSizes Solubilityall of the latices in question are soluble in aqueousbases such as aqueous ammonium hydroxide to provide sizing solutions.

Sizing Solutionsprepared from the latices of Example 1 to 5 and 7 to 10have Brookfield viscosities in the range of from 1 to 300 centipoises at4 to 5% solids allowing ease of application to the yarn.

Wet tensile strength-films prepared from the latices of the presentinvention have wet tensile strength in excess of 1000 p.s.i. and thenecessary toughness and film integrity required in water jet sizes.

Percent elongationthese values further indicate that the latices inquestion have the necessary film toughness required in water jet sizes.

Adhesion-the latices of Examples 1 to 5 and 7 to 10 have been tested andfound to have good adhesion to the following yarnsfilaments, acetate,polyester, rayon, texturized polyester, nylon, spun polyester, cotton,rayon and wool, acetate, nylon and blends thereof.

Resolubility in mild alkalidried films of the latices in question arereadily soluble in tetrasodium pyrophosphate-surfactant solutions whichindicates that the size is easily removed from the woven fabric. Thesize is also soluble in chlorinated solvents used in desizingoperations.

Size efficiency-is a measure of the amount of size addon required in agiven operation. The add-on is the amount of size that must be appliedto the yarn in order to permit it to be woven on a loom. In general, theless size add-on required, the more efiicient the size. Sizes preparedfrom the latices of the present invention have excellent efiiciency asis indicated by the following -Examples 22 to 24.

EXAMPLE 22 A latex composition is prepared as in Example 10 above usingmonomeric charge of 90.5% by weight of vinyl acetate, 5% by weight ofdimethyl maleate and 4.5% by weight of acrylic acid. The resultinglatex, wherein the polymer component has a specific viscosity of 2.7, isdissolved in aqueous ammonium hydroxide to give a 5.0% solids solutionhaving a pH of 9.0.

The sizing solution at F. is applied to a 150 denier, 41 monofilament,low twist bright acetate yarn on a commercial eleven can slasher at arate of 90 yards per minute for a size add-on of 2.1%. Drying cantemperatures on the slasher are 185/200/ 200/215/220/220/230/220/ 210/80/ F. respectively. The split is very easy, and no ends break out atstart-up.

The sized Warp is entered into a Nissan Prince water jet loom, where at40 picks per minute the weaving operation runs at very high efiiciency,(98%) with no second quality fabric produced. The woven fabric has a dryappearance in contrast to warps woven with lower M.W. (specificviscosity of 0.7) materials which become wet and slimy. Successive warpsshows the same excellent performance. This fabric was desized in aconventional process by scouring in tetrasodium pyrophosphate wettingagent baths. The size is also removable in a chlorinated solventscouring process.

EXAMPLE 23 Example 22 is repeated here using a latex with a specificvlscosity of 2.73. This latex is dissolved with aqueous ammoniumhydroxide to give a 4.5 solids solution having a pH of 9.2. The size isapplied to a 75 denier 20 monofilament low twist (75/20/LT) brightacetate yarn on a seven can slasher. The slasher is run at 25 yards perminute at a size add-on of 1.9% using drying can temperatures of 210/160/ 150/ cold, respectively. The warp slits very easily and weaves atvery high efficiency to give good quality fabric which is desized as inExample 22.

EXAMPLE 24 This example is set forth to illustrate the exceptionalefliciency of the sizes prepared according to the processes of thepresent invention. Example 22 is repeated here using a latex with aspecific viscosity of 2.73. This latex is dissolved with aqueousammonium hydroxide to give a 4.5% solids solution having a pH of 9.2.The size is applied to a 150 denier, 40 monofilament, 0.8 twist (150/40/0.8) bright acetate yarn on a seven can slasher at 55 yards perminute at a size add-on of 1.6%. Drying can temperatures are190/210/210/210/ l90/cool. The warp splits very easy, and no ends breakout during the sizing operation. The warp weaves at very high efliciencyto give good quality fabric which is desized as in Example 22. Theadd-on rate (1.6%) used in this example is unusually low when comparedto the sizes of the prior art which must be used in much larger amounts.

Sizes which are obtained from polymers prepared by the processes of thepresent invention are compared to commercially available textile sizes.The results of these comparisons is set forth below. In these tests thetoughness value is the product of tensile times elongation.

Various sizes in the form of ammonium salts are applied to acetate andpolyester filaments under water jet conditions. The size is tested forwet tensile, wet elongation, wet toughness and wet adhesion. The resultsare tabulated in the following Table IV.

10 Size A, which is obtained from a latex prepared accord ing to theprocesses of the present invention, exhibits greater toughness andbetter adhesion than the sizes of the prior art.

LOOM FINISH ACETATE AND NYLON SIZES TABLE IV.TESTS ON WATER JET SIZE ONACETATE AND POLYESTER FILAMENT Percent Tough- Adhesion Specific Tensileelonganess Size Composition 1 viscosity (p.s.i.) tion (X100 AcetatePolyester A VA/DMM/AA 90.5/5/45-.- 2.36 2,150 540 116 Excellent. Good.

. VA/DBM/AA 91.65/5/3.35. 1.79 700 250 17.5 Poor Poor.

CA 96 4 750 200 15 Good Good.

700 400 28 Fair-.. Poor. 540 3. 2 Good. Do. 0 0 Poor" Do. 480 200 9.6Good Excellent.

1 Values are in weight percent.

No'rE.-VA=vinyl acetate; DMM=dirnethyl maleate; DBM=dibutyl maleate;MMM=monon1ethyl malcate; MIBM-monoisobutyl maleate; AA=aerylic acid;CA=erotonic acid; MA=maleic anhydride;

AE =acrylate ester.

Size A is obtained from a latex that is prepared according to theprocesses of the present invention. Sizes C to G are commerciallyavailable sizes which are representative of the prior art. Note thatSize A has good to excellent adhesion and is at least five times (5X)tougher than the sizes of the prior art.

CONVENTIONAL SIZE ON ACETATE, RAYON AND TEXTURIZED POLYESTER Varioussizes in the form of sodium salts are applied to filament acetate, rayonfilament and texturized polyester. The sizes are then tested underconditions of RH. for tensile, elongation, toughness and adhesion. Theresults are tabulated in the following Table V.

CONVENTIONAL SIZE ON ACETATE, RAYON AND TEXTURIZED POLYESTER AdhesionPercent Tensile, elonga- Tough- Poly- (p.s.i tion ness Acetate Rayonester 3,060 370 113 44 High 20 1,530 300 47 36 do. 12 2,000 200 40 30410.... 18 2, 250 30 30 do. 14 1,400 400 27 do 16 l Compositions A to Fare the same as in Table IV above except that A has a specific viscosityof 2.94. G is a commercial gelatin size. H is an cquimolar styrenemaleicanhydride copolymer. A

2 Numerical values are pounds required to break x inch lap oints.

TABLE VI.LOOM FINISH ACETATE AND NYLON SIZES Percent Tougn- Adhesion(lbs.)

. Tensile elonganess Size 1 (p.s.i.) tion (X10 Acetate Nylon A 3, 450370 128 19 13 2, 060 230 47 40 9 1, 660 130 22 27 11 2, 260 26 14 16 E3, 820 20 8 14 11 Polyvinyl alcohol- 2, 000 500 100 15 1 Compositions Ato E same as in Table IV above except that A has a specific viscosity of2.66. The polyvinyl alcohol used is a partially hydrolyzed low molecularweight polymer which cannot be used as a loom finish because of itswater sensitivity.

2 Tested as in Table V.

Once again, Size A, which is representative of the sizes of the presentinvention, shows superior toughness. The adhesion of this size toacetate and nylon further indicate its utility as a textile size.

SPUN SIZES FOR AQUEOUS REMOVABLE AND SOLVENT REMOVABLE APPLICATIONSTABLE VII-SPUN SIZES FOR AQUEOUS REMOVABLE AND SOLVENT REMOVABLEAPPLICATIONS 1 Compositions A to E same as in Table IV above except thatA has a specific viscosity of 3.71 and a VA/DMM/AA composition 0190/5/5weight partially hydrolyzed polyvinly ht. PVOH-PH is a high molecular byweig 01 PVC -FH 15 a high molecular weight fully hydrolyzed polyvinylalcohol. CMC/binder is a blend of carboxymethylcellulose and an acrylatebinder. Starch/binder is a blend of starch and an acrylate binder.

2 Adhesion tests are run on a }4 square inch polyester to wood boardbond.

3 The aqueous solution contains a tetrasodaum pyrophospate wetting agentcombination. The organic solvent used is trichloroethylene.

Size A which is representative of the sizes of the present inventionexhibits excellent toughness and adhesion. Moreover, this material isremovable in conventional aqueous desizing operations as well as inorganic solvent desizing operations. This latter feature is especiallyimportant where water shortage or water pollution problems exist.

Another feature of the present invention is the fact that the polymericmaterial may be dissolved in organic solvents to form a size. Thisfeature is especially desirable in certain applications wherein solventsize removal techniques are also employed. In such applications thepolymer solids are recovered from the latex, using conventional means.The polymer solids are then dissolved in an organic solvent to form thetextile size and the size in the form of an organic solvent solution isapplied. Size removal may be accomplished using aqueous alkali ororganic solvent methods.

Preferred organic solvents used in preparing the sizes are alcohols,ketones, esters and aromatic solvents. Especially preferred arechlorinated aliphatic hydrocarbons such as methylene chloride, methylenebromide, chloroform, bromoform, ethylene dichloride, ethylene dibromide,ethylidene cloride, ethylidene bromide, s-tetrachloroethane,hexachloroethane, s-dichloroethylene, 1,1,1- trichloroethane,1,1,2-trichloroethane, trimethylene bromide, trichlorobromoethane,trichloromethane, 1,2,3-trichloropropane, 1,1,2-trichloropropane,trifluoro- 1,2-tribromoethane, trifluoro-1,1,2-tribromoethane,trifiuoro-1,l, 2-trichl0roethane, 2,2-dichlorol-bro-moethane,1,3-dichloro-2-methyl-propane, 1,2-dichloro 2-methyl-propane,1,1-diiodoethane trichloroethylene and the like. Chlorinated aliphaticliquid hydrocarbons are preferred in the practice of this inventionbecause of their generally lower cost, greater availability and the easewith which these solvents may be handled.

Recovery of the polymer solids from the latex is achieved by thefollowing methods among others: stripping off the Water at atmosphere orsubatmosphere pressure; coagulating the latex by the addition of onevolume of acetone to three volumes of latex at room temperature,recovering the curdy precipitate and drying; adding one volume of latexto three volumes of ethyl acetate, collecting the hard precipitate anddrying; adding a strong acid-e.g. H 50 HCL or acetic to the latex to apH of 1-2, and heating to 60-65" C., recovering the precipitate anddrying; and adding 10% sodium chloride (as a concentrated solution) tothe latex and heating to 60-65 C., recovering the precipitate anddrying. The second and third methods are examples of the generalprocedure of adding an organic solvent to strip the protectivesurfactant from the latex particle causing the polymer to precipitate.

Obviously other organic solvents can be used. The preferred solvents arethose which give a hard or slightly swollen material which is convenientto handle and dry.

In all cases the recovered dried polymer is dissolved in the chlorinatedhydrocarbon solvent to give a solids content in the range of 1 to 25%for use as a sizing solution. The sizing solution may also containconventional adjuvants, lubricants, defoamers and plasticizers withoutdeparting from the scope of the invention.

EXAMPLE 25 This example is set forth to demonstrate the preparation andapplication of a solvent size of an interpolymer of vinyl acetatedimethyl maleate and acrylic acid.

The interpolymer latex of Example 23 is coagulated by addition of thevolume of acetone to three volumes of latex at room temperature. A curdyprecipitate forms. It is separated from the aqueous solution, dried outand dissolved in trichloroethylene to give a 8.4 percent solidssolution. The solution viscosity is 82 cps at 70 C. This size solutionis applied at 82 C. to a 25/1 50/50 polyester/cotton yarn at 20 yardsper minute on an experimental solvent slasher. The size add-on is 10.3%.The warp is woven on a loom at 176 picks per minute at high efiiciencyto give a high quality fabric. This weaving performance is similar tothat achieved with a warp sized with 23.6% starch. The size iscompletely removed by scouring with boiling trichloroethylene.

What is claimed is:

1. A process for the preparation of a textile size which comprises:

A. Interpolymerizing from 83 to by weight of vinyl acetate, from 2 to10% by weight of a dialkyl maleate selected from the group consisting ofdimethyl maleate and diethyl maleate and from 3 to 7% by Weight ofacrylic acid based on the total Weight of the monomers, in a latexpolymerization system using a surfactant which is a phosphate ester ofan alkyl phenol-ethylene oxide condensate wherein the alkyl groupcontains 7 to 11 carbon atoms;

B. Recovering the resulting latex interpolymer, and

C. Dissolving the resulting latex interpolymer in a chlorinatedaliphatic hydrocarbon solvent to form the textile size.

2. The process as in claim 1 wherein the amount of vinyl acetate is inthe range of from 87.5 to 91%, the amount of dialkyl maleate is in therange of from 5 to 7.5% by weight and the amount of acrylic acid is inthe range of from 4 to 6% by weight.

3. The process as in claim 1 wherein the dialkyl maleate is dimethylmaleate.

4. The process as in claim 1 wherein the surfactant is a phosphate esterof tertiary octyl phenol-ethylene oxide condensate.

5. The process as in claim 1 wherein the surfactant is a phosphate esterof nonyl phenol-ethylene oxide condensate.

6. The process as in claim 1 wherein the polymerization temperature isin the range of from 40 to 60 C.

7. A process for the preparation of a textile size which comprises:

A. Interpolymerizing at a temperature in the range of from 40 to 60 C.from 87.5 to 91% by weight of vinyl acetate, from 5 to 7.5 by weight ofa dimethyl maleate and from 4 to 6% by weight of acrylic acid based onthe total weight of the monomers, in a latex polymerization system usinga surfactant which is a phosphate ester of an alkyl phenolethylene oxidecondensate wherein the alkyl group contains 7 to 11 carbon atoms;

B. Recovering the resulting latex interpolymer, and

C. Dissolving the resulting latex interpolymer in a chlorinatedaliphatic hydrocarbon solvent.

8. The process as in claim 7 wherein the surfactant is a phosphate esterof tertiary octyl phenol-ethylene oxide condensate.

9. The process as in claim 7 wherein the surfactant is a phosphate esterof nonyl phenol-ethylene oxide condensate.

10. The process as in claim 1 wherein the chlorinated hydrocarbonsolvent is selected from the group consisting of methylene chloride,cholorform, ethylene dichloride, 1,1,l-trichloroethane,1,1,2-trichloroethane and trichloro ethylene.

11. process for the preparation of a textile size which comprises:

A. Interpolymerizing from 83 to 95% by weight of vinyl acetate, from 2to 10% by weight of a dialkyl maleate selected from the group consistingof dimethyl maleate and diethyl maleate and from 3 to 7% by weight ofacrylic acid based on the total weight of the monomers, in a latexpolymerization system containing a phosphate ester of an alkylphenol-ethylene oxide condensate wherein the alkyl group contains 7 to11 carbon atoms and a co-sur factant selected from the group consistingof alkylaryl sulfonates, fatty alcohol sulfates and dialkylsulfosuccinates,

B. Recovering the resulting latex interpolymer, and

C. Dissolving the resulting latex interpolymer in a chlorinatedaliphatic hydrocarbon solvent to form the textile size.

12. The process as is claim 11 wherein the amount of vinyl acetate is inthe range of from 87.5 to 91%, the amount of dialkyl maleate is in therange of from to 7.5% by weight and the amount of acrylic acid is in therange of from 4 to 6% by weight.

13. The process as in claim 11 wherein the polymerization temperature isin the range of from to C.

14. The process as in claim 11 wherein the chlorinated aliphatichydrocarbon solvent is selected from the group consisting of methylenechloride, chloroform, ethylene dichloride, 1,1,1-trichloroethane,1,1,2-trichl0roethane and trichloroethylene.

15. A process for the preparation of a textile size which comprises:

A. Preparing an aqueous latex of solids content in the range of 15 topercent by weight by inter polymerizing from 83 to by weight of vinylacetate. from 2 to 10% by Weight of a dialkyl maleate selected from thegroup consisting of dimethyl maleate and diethyl maleate and from 3 to7% by Weight of acrylic acid based on the total weight of the monomers,at a temperature in the range of 40 to 60 C., in a latex polymerizationsystem with a surfactant which is a phosphate ester of an alkylphenol-ethylene oxide condensate wherein the alkyl group contains 14 7to 11 carbon atoms, the surfactant comprising between 1 and 4% by weightof the total weight of the latex and a cosurfactant selected from thegroup consisting of alkylaryl sulfonates, fatty alcohol sulfates anddialkyl sulfosuccinates, comprising between 0.1 and 0.3% by weight ofthe total of the latex, wherein the resulting interpolymer has aspecific viscosity in in the range of 1.2 to 12.0, B. Recovering theresulting latex interpolymer, and C. Dissolving the resulting latex in achlorinated aliphatic hydrocarbon solvent to form the textile size. 16.The process as in claim 15, wherein the surfactant is selected from thegroup consisting of phosphate esters of tertiary octyl phenol-ethyleneoxide condensate and nonyl phenol-ethylene oxide condensate.

References Cited UNITED STATES PATENTS 2/1973 Corey et a1 260--29.6 TA3/1973 Corey et a1 26033.8 UA

LUCILLE M. PHYNES, Primary Examiner U.S. Cl. X.R.

